Sputtered carbon material has been receiving much attention as a solid lubricant coating owing to its high hardness and low coefficient of friction. However, its relatively low wear resistance performance when applied on a ductile substrate has limited its use in certain applications. In this work, a porous WS2 sublayer was introduced to the sputtered carbon-based nanoscale multilayer coating to improve its tribological properties. The microstructural, mechanical and tribological properties of the nanoscale C/WS2 multilayer coating were systematically investigated using various analytical techniques. Through structural optimization, a durable coating with excellent wear resistance and low frictional performances could be attained for a ductile steel substrate. The excellent toughness allowed the coating to deform with the ductile substrate without fracturing during contact sliding process. Furthermore, the first self-destruction and then recombination behaviors of dense/porous-coupled nanoscale multilayer coating as well as the selective release of carbon component to the contact interface driven by the frictional interaction aided in maintaining low friction. As a result, the nanoscale multilayer coating showed approximately 100-fold greater wear resistance than that of pure hard carbon coating on a ductile steel substrate.